Non-thermoset thermally stable capped epoxy resin compositions

ABSTRACT

A heat stable, non-thermoset epoxy resin composition is disclosed which comprises reacting (A) a mixture containing (1) a relatively high molecular weight epoxy resin and (2) a relatively low molecular weight epoxy resin with (B) a monohydric phenol, a monocarboxylic acid or anhydride thereof or a monohydric alcohol. The composition does not exhibit an excessive viscosity increase at elevated temperatures making it particularly suitable for use in highway marking paint applications.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of copending application Ser.No. 715,305 filed Mar. 25, 1985 which is a continuation-in-part ofapplication Ser. No. 677,781 filed Dec. 4, 1984 (both now abandoned).

BACKGROUND OF THE INVENTION

The present invention concerns non-thermoset, thermally stable, cappedepoxy resin compositions and coatings prepared therefrom.

Thermoplastic (non-thermoset) epoxy resins have been employed in theformulation of highway, pavement, marking paints as disclosed by J. M.Dale in DEVELOPMENT OF LANE DELINEATION WITH IMPROVED DURABILITY, ReportNo. FHWA-RD-75-70, July 1975. The paint formulations are maintained atelevated temperatures, about 450° F. (232° C.), during application.While they provide an excellent high marking paint in terms of abrasiveresistance, they are deficient in terms of applicability since theyexhibit a substantial increase in viscosity while being maintained atthe application temperature.

The present invention provides a non-thermoset epoxy resin whichexhibits a much reduced viscosity increase at elevated temperatures,i.e. more stable.

SUMMARY OF THE INVENTION

The present invention pertains to a thermally stable, non-thermosetresin having a Mettler softening point of from about 75° C. to about110° C., preferably from about 88° C. to about 95° C. and a BrookfieldThermosel viscosity at 450° F. of from about 150 cps to about 260 cps,preferably from about 200 cps to about 250 cps prepared by reacting inthe presence of an effective quantity of a suitable catalyst

(A) a mixture comprising

(1) from about 65 to about 80, preferably from about 73 to about 76,percent by weight of a relatively high molecular weight epoxy resinhaving an average of more than one vicinal epoxide group per moleculeand an epoxide equivalent weight (EEW) of from about 1600 to about 2300,preferably from about 1700 to about 1900; and

(2) from about 35 to about 20, preferably from about 27 to about 24,percent by weight of a relatively low molecular weight epoxy resinhaving an average of more than one vicinal epoxide group per moleculeand an EEW of from about 180 to about 225, preferably from about 180 toabout 190;

wherein the equivalent weight of components (1) and (2) are calculatedon the basis that the epoxy resin contains only carbon, oxygen andhydrogen atoms even though it may contain other atoms; with

(B) at least one monofunctional material selected from monohydricphenols, aliphatic alcohols having from about 3 to about 8 carbon atoms,aliphatic monocarboxylic acids, said anhydrides having from about 12 toabout 20 carbon atoms, anhydrides of aliphatic monocarboxylic acidshaving from about 4 to about 8 carbon atoms, aromatic substitutedaliphatic monocarboxylic acids having from about 8 to about 10 totalcarbon atoms and combinations thereof; and

wherein components (A) and (B) are employed in quantities which providean equivalent ratio of component (B) to component (A) of from about0.87:1 to about 1.1:1, preferably from about 0.95:1 to about 1.1:1except when component (B) is an aliphatic alcohol, then the equivalentratio of component (B) to component (A) is from about 3.5:1 to about20:1, preferably from about 4:1 to about 10:1, most preferably fromabout 4:1 to about 6:1, with the proviso that the amount of components(A-1) and (A-2) and the ratio of components (A) and (B) are such thatthe desired Mettler softening point and Brookfield Thermosel viscosityare obtained.

The present invention also pertains to a paint formulation comprising

(A) the aforementioned thermally stable non-thermoset resin; and

(B) at least one of

(1) one or more pigments or dyes; or

(2) one or more fillers.

DETAILED DESCRIPTION OF THE INVENTION

It is desirable in the highway marking area to have a thermoplastic(non-thermoset) material that may be applied to the highway withexisting equipment. The present invention provides a non-thermosetmaterial with the additional benefit of the capability of being appliedwith existing equipment. In addition to being thermally stable, thehighway marking material (without fillers, pigments, glass beads orother additives) should have a softening point of about 75° C. to about110° C. and a viscosity at 232° C. of from about 150 cps to about 260cps. This viscosity range is necessary to have a material which whenformulated with fillers, pigments, glass beads or other additives can beapplied with existing conventional equipment and also decreases oreliminates the settling of the fillers, pigments, glass beads or otheradditives before application to the pavement surface. Another aspect ofviscosity is that if the viscosity varies from the above cited ranges,undesired settling of the reflective glass beads can occur afterapplication. The material should have a softening point above about 75°C. so that it can be applied in warm climates. Materials having asoftening point substantially below about 75° C. have a tendency tobecome tacky and pick up road grime and become off-color which leads tolimited visibility. At softening points greater than about 110° C., thematerial becomes difficult to melt and the viscosity exceeds the limitsof the application equipment.

Suitable epoxy resins which can be employed in the process of thepresent invention include, for example, those represented by theformulas ##STR1## wherein each A is independently a divalent hydrocarbylgroup having from 1 to about 10, preferably from 1 to about 6 carbonatoms; each R is independently hydrogen or a hydrocarbyl group havingfrom 1 to about 4 carbon atoms; each X is independently hydrogen, ahalogen, preferably chlorine or bromine, or a hydrocarbyl group havingfrom 1 to about 12 carbon atoms; n has a value of zero or 1 and n' hasan average value of from about 0.07 to about 15, preferably from about0.07 to about 12.2.

Particularly suitable epoxy resins include the glycidyl ethers ofpolyhydric phenols such as resorcinol, catechol, hydroquinone, bisphenolA, bisphenol F, mixtures thereof and the like.

Suitable polyhydric phenolic compounds which can be employed to preparerelatively high molecular weight epoxy resins by advancing a relativelylow molecular weight epoxy resin include, for example, those representedby the formulas ##STR2## wherein A, X and n are as hereinbefore defined.

Particularly suitable polyhydric phenolic materials include, forexample, resorcinol, catechol, hydroquinone, bisphenol A, bisphenol F,mixtures thereof and the like.

Suitable monohydric phenolic compounds include, for example, thoserepresented by the formula ##STR3## and each X' is independentlyhydrogen, a halogen, preferably chlorine or bromine, or a hydrocarbyl orhydrocarbyloxy group having from 1 to about 12 carbon atoms.

Particularly suitable monohydric phenolic materials include, forexample, phenol, alkylphenols, such as p-nonylphenol, p-t-butylphenol,o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol and3,5-xylenol, alkoxyphenols such as, for example, o-methoxyphenol,p-methoxyphenol, combinations thereof and the like.

Suitable monohydric alcohols which can be employed herein include, forexample, methanol, ethanol, propanol, isopropanol, butanol, pentanol,hexanol, heptanol, octanol, combinations thereof and the like.

Suitable monocarboxylic acids which can be employed herein include, forexample, lauric acid, myristic acid, palmitic acid, stearic acid, oleicacid, phenylacetic acid, methoxyphenyl acetic acid, methoxyphenoxyacetic acid, toluic acid, combinations thereof and the like.

Suitable anhydrides of monocarboxylic acids which can be employed hereininclude, for example, acetic anhydride, propionic anhydride, butyricanhydride, combinations thereof and the like.

Suitable catalysts for effecting the reaction between the epoxy resinand the phenolic hydroxyl-containing materials include, for example,those disclosed in U.S. Pat. Nos. 3,306,872; 3,341,580; 3,379,684;3,477,990; 3,547,881; 3,637,590; 3,843,605; 3,948,855; 3,956,237;4,048,141; 4,093,650; 4,131,633; 4,132,706; 4,171,420; 4,177,216 and4,366,295, all of which are incorporated herein by reference.

Particularly suitable catalysts are those quaternary phosphonium andammonium compounds such as, for example, ethyltriphenylphosphoniumchloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphoniumiodide, ethyltriphenylphosphonium acetate, ethyltriphenylphosphoniumdiacetate (ethyltriphenylphosphonium acetate.acetic acid complex),tetrabutylphosphonium chloride, tetrabutylphosphonium bromide,tetrabutylphosphonium iodide, tetrabutylphosphonium acetate,tetrabutylphosphonium diacetate (tetrabutylphosphonium acetate.aceticacid complex), butyltriphenylphosphonium tetrabromobisphenate,butyltriphenylphosphonium bisphenate, butyltriphenylphosphoniumbicarbonate, benzyltrimethylammonium chloride and tetramethylammoniumhydroxide.

Other suitable catalysts include tertiary amines such as, for example,triethylamine, tripropylamine, tributylamine, 2-methylimidazole,benzyldimethylamine, N-methyl morpholine, mixtures thereof and the like.

Suitable pigments which can be employed herein include any which willprovide the coating with the deisred color such as, for example,titanium dioxide, lead chromate, zinc chromate, chrome green,pthalocyamine green and blue, iron oxide, combinations thereof and thelike.

Suitable fillers which can be employed herein include, for example,calcium carbonate, talc, glass beads, powdered or flaked zinc oralumina, powdered or flaked glass, colloidal silica, combinationsthereof and the like.

The following examples are illustrative of the present invention, butare not to be construed as to limiting the scope thereof in any manner.

In the examples and comparative experiments, the viscosities areBrookfield Thermosel viscosities and the softening points are Mettlersoftening points.

ABRASION TEST

The abrasion test was conducted on a Teledyne Taber Abraser Model No.503 using CS-10 grind stones with a 1 kg mass added to each grind stonearm. The rotation speed was 1.2 cycles per second. The grind stones werecleaned by letting the stones roll over sand paper for 10 cycles thenthe sand paper was replaced with the sample to be evaluated. The testsample mass was determined before and after abrasion to determine themass loss. The samples were prepared by mixing the test resin withfiller, pigment and glass beads. This mixture was placed into a 200° C.oven and melted and mixed together. This mixture was poured onto apreheated 4"×4"×20 gauge (101.6 mm×101.6 mm×0.95 mm) cold rolled steelpanel and then placed in a 200° C. oven for 5 min. (300 s). The panelwas then removed from the oven and allowed to cool overnight prior totesting.

EXAMPLE 1 A. Preparation of Capped Epoxy Resin

To a reaction vessel equipped with a means for stirring and temperaturecontrol was added 37.1 lbs (16.8 kg, 10.2 gram epoxy equiv.) of adiglycidyl ether of bisphenol A having an epoxide equivalent weight(EEW) of 1646, 18 lbs (8.2 kg, 43.8 gram epoxy equivalents) of adiglycidyl ether of bisphenol A having an EEW of 187, 23 lbs (10.4 kg,47.3 gram hydroxyl equiv.) of nonyl phenol and 0.077 lbs (0.169 kg) of a70% solution of ethyltriphenyl phosphonium acetate.acetic acid complexin methanol. The ratio of equiv. of nonyl phenol to epoxy equiv. was0.88:1. The mixture was heated to 160° C. at a rate of 1.5° C./min.(0.025° C./s) and maintained thereat for 2 hours (7200 s). The resultantproduct was a colorless to pale yellow resin, solid at room temperature,had a softening point of 81° C. and a viscosity of 150 cps (0.15 pa.s)at 450° F. (232° C.).

B. Preparation of Traffic Marking Paint

A mixture was prepared at 200° C. of the following components:

1. 100 parts by weight of the resin from (A) above

2. 20 parts by weight of TiO₂

3. 20 parts by weight of CaCO₃

4. 28 parts by weight of 200 mesh glass beads

Components 1, 2 and 3 were mixed under high shear conditions. Component4 was mixed at low speeds.

The properties of the traffic paint formulation are given in thefollowing Table.

C.

For comparative purposes, a similar paint formulation was prepared froman epoxy resin mixture without nonyl phenol capping. The formulation wasas follows:

1. 40 parts by weight of a diglycidyl ether of bisphenol A (DGEBA)having an EEW of 186-192

2. 60 parts by weight of a DGEBA having an EEW of 1600-2000

3. 20 parts by weight of TiO₂

4. 20 parts by weight of CaCO₂

5. 28 parts by weight of 200 mesh glass beads

The properties are given in the following Table I.

                  TABLE I                                                         ______________________________________                                                       Formulation                                                                   1-B       Formulation                                                         Present   1-C                                                                 Invention Comparative                                          ______________________________________                                        Mettler Softening Point, °C.                                                            89          77                                               Cold flow at 25° C.                                                                     No          Yes                                              Initial Viscosity @ 450° F.                                                             505/0.505   480/0.480                                        (232° C.), cps/pa.s                                                    Viscosity after 8 hours                                                                        510/0.51    1500/1.5                                         (28800 s) at 450° F.                                                   (232° C.), cps/pa.s                                                    Condition after 24 hours                                                                       slight      gelled,                                          (86400 s) at 450° F. (232° C.)                                                   yellowing   brown                                            ______________________________________                                    

EXAMPLE 2 A. Preparation of Non-Capped Epoxy Resin Blend (Epoxy ResinBlend)

To a reaction vessel equipped with a means for stirring, nitrogen purgeand temperature control was added 725.2 g (3.9 epoxy equiv.) of adiglycidyl ether of bisphenol A having an epoxide equivalent weight(EEW) of 186, 374.8 g (3.29 equiv.) of bisphenol A and then heated to90° C. at which time 1.69 g (0.003 mole) of a 70% solution ofethyltriphenyl phosphonium acetate.acetic acid complex in methanol wasadded. The temperature was increased to 150° C. and then the reactionmass exothermed to 206° C. The temperature was maintained at 190° C. for1 hour (3600 s). The percent epoxide was 2.48 (1734 EEW). To thismaterial was added 528.4 g (2.84 epoxy equiv.) of a diglycidyl ether ofbisphenol A having an EEW of 186, and the temperature decreased to 150°C. This product had a percent epoxide of 9.1 (473 EEW). The mixturecontained 67.6 wt.% of a 1734 EEW epoxy resin and 32.4 wt.% of a 186 EEWepoxy resin.

B. Preparation of Capped Epoxy Resin

To a reaction vessel equipped with a means for stirring and temperaturecontrol was added 150 g (0.32 epoxy equiv.) of epoxy resin blendprepared in A above, 100 g (1.35 mole) of n-butanol and heated to 50° C.whereupon 0.3 g (0.002 mole) of boron trifluoride etherate was added.The equiv. ratio of n-butanol to epoxy equiv. was 4.22:1. Thetemperature was increased to 60° C. and maintained at 60°-63° C. for3.17 hours (11412 s), heated to 200° C. and vacuum stripped for 2.08hours (7488 s). The product was dried in a vacuum oven at 160° C. for 2hours (7200 s). The viscosity was 189.5 cps (01895 pa.s) at 450° F.(232° C.) and had a softening point of 78° C.

EXAMPLE 3

To a reaction vessel equipped with a means for stirring and temperaturecontrol was added 97 g of propylene glycol monomethyl ether acetate, 8 g(0.078 mole) of acetic anhydride, 70 g (0.074 epoxy equiv.) of a 50%solution of epoxy resin blend prepared in Example 2A in propylene glycolmonomethyl ether acetate and 0.25 g (0.0009 mole) of a 70% solution ofethyltriphenyl phosphonium acetate.acetic acid complex in methanol. Theratio of equiv. of acetic anhydride to epoxy equiv. was 1.05:1. Thetemperature was increased to 120° C. and maintained for 5.2 hours(18,720 s). A portion of the solvent was removed by heating at 145° C.for about 0.5 hour (1800 s). The resultant material was then placed on ahot plate for 1 hour (3600 s) at 206° C. The product was dried in avacuum oven at 160° C. for 2 hours (7200 s). The viscosity was 154 cps(0.154 pa.s) at 450° F. (232° C.) and had a softening point of 79.5° C.

EXAMPLE 4

To a reaction vessel equipped with a means for stirring and temperaturecontrol was added 197 g (1.042 epoxy equiv.) of a diglycidyl ether ofbisphenol A having an EEW of 189 and 103 g (0.904 equiv.) of bisphenolA. After heating the mixture to 90° C., 0.46 g (0.0009 mole) of a 70%solution of tetra n-butylphosphonium acetate.acetic acid complex inmethanol was added. The temperature was increased to 180° C. andmaintained thereat for 1.25 hours (4500 s). The EEW of the resultantadvanced epoxy resin was 2251. To this material was added 100 g (0.529epoxy equiv.) of a diglycidyl ether of bisphenol A having an EEW of 189and 178 g (0.654 equiv.) of stearic acid. The ratio of equiv. of stearicacid to epoxy equiv. was 0.996:1. The material was reacted an additional2.08 hours (7488 s) at 180° C. The viscosity was 228 cps (0.228 pa.s) at450° F. (232° C.) and had a softening point of 106.9° C.

EXAMPLE 5

To a reaction vessel equipped with a means for stirring and temperaturecontrol was added 197 g (1.042 epoxy equiv.) of a diglycidyl ether ofbisphenol A having an EEW of 189 and 103 g (0.904 equiv.) of bisphenolA. After heating the mixture to 90° C., 0.46 g (0.0009 mole) of a 70%solution of tetra n-butylphosphonium acetate.acetic acid complex inmethanol was added. The temperature was increased to 180° C. andmaintained thereat for 1.37 hours (4932 s). The EEW of the resultantadvanced epoxy resin was 2205. To this material was added 100 g (0.529epoxy equiv. of a diglycidyl ether of bisphenol A having an EEW of 189and 131.2 g (0.656 equiv.) of lauric acid. The ratio of equiv. of lauricacid to epoxy equiv. was 0.986:1. The material was reacted an additional1.78 hours (6408 s) at 180° C. The viscosity was 247 cps (0.247 pa.s) at450° F. (232° C.) and had a softening point of 79.7° C.

EXAMPLE 6

The uncapped epoxy resin blend of Example 2A and the capped epoxy resinsprepared in Examples 3, 4 and 5 were subjected to a thermal stabilitytest. The results are given in the following Table II.

                  TABLE II                                                        ______________________________________                                        THERMAL STABILITY TEST                                                        Test Temperature 450° F. (232° C.)                                                            VISCOSITY                                       EPOXY RESIN TIME AT 450° F. (232° C.)                                                         cps/pa.s                                        ______________________________________                                        Epoxy Resin Blend*                                                                        Initial           209/0.209                                       of Ex. 2A   7 hours (25,200 s)                                                                              538/0.538                                       Example 3   Initial           154/0.154                                                   7 hours (25,200 s)                                                                              173/0.173                                       Example 4   Initial           228/0.228                                                   7 hours (25,200 s)                                                                              231/0.231                                       Example 5   Initial           247/0.247                                                   7 hours (25,200 s)                                                                              249/0.249                                       ______________________________________                                         *Not an example of the present invention.                                

EXAMPLE 7

Abrasion tests were conducted on two formulations as follows:

FORMULATION A

To a glass bottle was added 30.3 g of the diglycidyl ether of bisphenolA having an EEW of 1721, 10.01 g of the diglycidyl ether of bisphenol Ahaving an EEW of 189, 10.99 g of 200 mesh (U.S. Standard Sieve Series)glass beads, 7.84 g of calcium carbonate, 7.85 g of titanium dioxide.The contents were melted at 200° in an oven and thoroughly mixed. Themixture was poured onto a cold rolled steel panel and cooled overnight.The resultant coating thickness was 1.968 mm. The formulation wassubjected to an abrasion test. The results are given in the followingTable III.

FORMULATION B

To a glass bottle was added 39.98 g of a mixture of 75% by weight of thediglycidyl ether of bisphenol A having an EEW of 1721 and 25% by weightof the diglycidyl ether of bisphenol A having an EEW of 189 which hadbeen reacted with nonyl phenol in an amount which provided an equivalentratio of nonyl phenol to epoxy resin of 1:1, 10.98 g of 200 mesh (U.S.Standard Sieve Series) glass beads, 7.84 g of calcium carbonate, 7.8 gof titanium dioxide. The contents were melted at 200° in an oven andthoroughly mixed. The mixture was poured onto a cold rolled steel paneland cooled overnight. The resultant coating thickness was 1.539 mm. Theformulation was subjected to an abrasion test. The results are given inthe following Table III.

                  TABLE III                                                       ______________________________________                                                   Formulation A*                                                                            Formulation B                                          Cycles     mass loss, mg                                                                             mass loss, mg                                          ______________________________________                                         0         0           0                                                       10        2.4         0.3                                                     20        6.1         2.0                                                     40        11.0        9.0                                                     60        15.8        10.4                                                    80        19.7        15.2                                                   100        25.1        18.4                                                   120        36.9        25.7                                                   140        38.1        26.3                                                   160        41.5        34.5                                                   180        51.4        35.4                                                   200        53.0        38.5                                                   220        57.5        39.4                                                   240        68.6        43.9                                                   260        74.1        48.3                                                   280        75.9        52.4                                                   300        78.6        60.1                                                   320        80.3        61.1                                                   340        N.T.**      65.1                                                   360        N.T.        69.4                                                   ______________________________________                                         *Not an example of the present invention                                      **N.T. means not tested                                                  

We claim:
 1. A paint formulation comprising(I) a thermally stable,non-thermoset resin having a Mettler softening point of from about 75°C. to about 110° C. and a Brookfield Thermosel viscosity at 450° F. offrom about 150 cps to about 260 cps prepared by reacting in the presenceof an effective quantity of a suitable catalyst(A) a mixturecomprising(1) from about 65 to about 80 percent by weight of arelatively high molecular weight epoxy resin having an average of morethan one vicinal epoxide group per molecule and an epoxide equivalentweight (EEW) of from about 1600 to about 2300; and (2) from about 35 toabout 20 percent by weight of a relatively low molecular weight epoxyresin having an average of more than one vicinal epoxide group permolecule and an EEW of from about 180 to about 225; wherein theequivalent weight of components (1) and (2) are calculated on the basisthat the epoxy resin contains only carbon, oxygen and hydrogen atomseven though it may contain other atoms; with (B) at least onemonofunctional material selected from monohydric phenols, aliphaticalcohols having from about 3 to about 8 carbon atoms, aliphaticmonocarboxylic acids having from about 12 to about 20 carbon atoms,anhydrides of aliphatic monocarboxylic acids, said anhydrides havingfrom about 4 to about 8 carbon atoms, aromatic substituted aliphaticmonocarboxylic acids having from about 8 to about 10 total carbon atomsand combinations thereof andwherein components (A) and (B) are employedin quantities which provide an equivalent ratio of component (B) tocomponent (A) of from about 0.87:1 to about 1.1:1) except that whencomponent (B) is an aliphatic alcohol, then the equivalent ratio ofcomponent (B) to component (A) is from about 3.5:1 to about 20:1; withthe proviso that the amount of components (A-1) and (A-2) and the ratioof components (A) and (B) are such that the desired Mettler softeningpoint and Brookfield Thermosel viscosity are obtained; and (II) at leastone of(a) one or more pigments; (b) one or more dyes; (c) one or morefillers; or (d) any combination thereof.
 2. A paint formulation of claim1 wherein component I has a Mettler softening point of from about 88° C.to about 95° C. and a Brookfield Thermosel viscosity at 450° F. of fromabout 200 cps to about 250 cps and components (A) and (B) are employedin quantities which provide an equivalent ratio of component (B) tocomponent (A) of from about 0.95:1 to about 1:1 except that whencomponent (B) is an aliphatic alcohol, then the atomic ratio ofcomponent (B) to component (A) is from about 4:1 to about 10:1.
 3. Apaint formulation of claim 1 wherein(i) component (A)(1) is an epoxyresin or a mixture of epoxy resins represented by the following formulaII ##STR4## wherein each A is independently a divalent hydrocarbyl grouphaving from 1 to about 10 carbon atoms; each R is independently hydrogenor a hydrocarbyl group having from 1 to about 4 carbon atoms; each X isindependently hydrogen, a halogen or a hydrocarbyl group having from 1to about 12 carbon atoms; n has a value of zero or 1 and n' has aaverage value from 10 to about 15; (ii) component (A)(2) is an epoxyresin or mixture of epoxy resins represented by formula II wherein A, R,X and n are as defined above and n' has an average value from about 0.07to about 0.39; and (iii) in component (B) said monohydric phenoliccompounds are represented by the following formula V ##STR5## whereineach X' is independently hydrogen, a halogen, or a hydrocarbyl orhydrocarbyloxy group having from 1 to about 12 carbon atoms.
 4. A paintformulation composition of claim 3 wherein(i) component (A)(1) is one ormore epoxy resins represented by formula II wherein each A is a divalenthydrocarbon group having from 1 to about 10 carbon atoms; each R ishydrogen, each X is hydrogen, chlorine or bromine; n has a value of 1and n' has an average value from about 10.77 to about 12.18; (ii)component (A)(2) is one or more epoxy resins represented by formula IIwherein each A is a divalent hydrocarbon group having from 1 to about 10carbon atoms; each R is hydrogen; each X is hydrogen, chlorine orbromine; n has a value of 1 and n' has an average value from about 0.07to about 0.14; and (iii) component (B) is selected from phenol,o-cresol, m-cresol, p-cresol, p-tert-butylphenol, p-nonylphenol,2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, o-methoxy phenol,p-methoxy phenol, stearic acid, lauric acid, acetic anhydride, butanolor a combination thereof.
 5. A paint formulation of claim 4 wherein(i)component (A)(1) is an epoxy resin represented by formula II whereineach A is a divalent hydrocarbyl group which has 3 carbon atoms and eachX is hydrogen; (ii) component (A)(2) is an epoxy resin represented byformula II wherein each A is a divalent hydrocarbyl group which has 3carbon atoms and each X is hydrogen; and (iii) component (B) isp-nonylphenol.
 6. A paint formulation of claim 2 wherein(i) component(A)(1) is an epoxy resin or a mixture of epoxy resins represented by thefollowing formula II ##STR6## wherein each A is independently a divalenthydrocarbyl group having from 1 to about 10 carbon atoms; each R isindependently hydrogen or a hydrocarbyl group having from 1 to about 4carbon atoms; each X is independently hydrogen, a halogen or ahydrocarbyl or hydrocarbyloxy group having from 1 to about 12 carbonatoms; n has a value of zero or 1 and n' has a average value from 10 toabout 15; (ii) component (A)(2) is an epoxy resin or mixture of epoxyresins represented by formula II wherein A, R, X and n are as definedabove and n' has an average value from about 0.07 to about 0.39; and(iii) in component (B) said monohydric phenolic compounds arerepresented by the following formula V ##STR7## wherein each X' isindependently hydrogen, a halogen, or a hydrocarbyl or hydrocarbyloxygroup having from 1 to about 12 carbon atoms.
 7. A paint formulation ofclaim 6 wherein(i) component (A)(1) is one or more epoxy resinsrepresented by formula II wherein each A is a divalent hydrocarbon grouphaving from 1 to about 6 carbon atoms; each R is hydrogen; each X ishydrogen; chlorine or bromine; n has a value of 1; and n' has an averagevalue from about 10.77 to about 12.18; (ii) component (A)(2) is one ormore epoxy resins represented by formula II wherein each A is a divalenthydrocarbon group having from 1 to about 10 carbon atoms; each R ishydrogen; each X is hydrogen, chlorine or bromine; n has a value of 1;and n' has an average value from about 0.07 to about 0.14; and (iii)component (B) is selected from phenol, o-cresol, m-cresol, p-cresol,p-tert-butylphenol, p-nonylphenol, 2,4-xylenol, 2,5-xylenol,3,4-xylenol, 3,5-xylenol, o-methoxy phenol, p-methoxy phenol, stearicacid, lauric acid, acetic anhydride, butanol or a combination thereof.8. A paint formulation of claim 7 wherein(i) component (A)(1) is anepoxy resin represented by formula II wherein each A is a divalenthydrocarbyl group which has 3 carbon atoms and each X is hydrogen; (ii)component (A)(2) is an epoxy resin represented by formula II whereineach A is a divalent hydrocarbyl group which has 3 carbon atoms and eachX is hydrogen; and (iii) component (B) is p-nonylphenol.
 9. A stripingpaint formulation comprising a paint formulation of claim 5 and glassbeads.
 10. A striping paint formulation comprising a paint formulationof claim 8 and glass beads.